KR101336744B1 - R­Fe­B RARE EARTH SINTERED MAGNET AND METHOD FOR PRODUCING SAME - Google Patents

Abstract

In the method for producing an R-Fe-B rare earth sintered magnet according to the present invention, first, a light rare earth element (RL) (at least one of Nd and Pr) is used as a main rare earth element (R: An R-Fe-B-based rare earth sintered magnet body having a main phase of R ₂ Fe ₁₄ B compound crystal grains contained as a rare earth element is prepared. Subsequently, while heating the sintered magnet body while supplying a heavy rare earth element (RH) (at least one selected from the group consisting of Dy, Ho and Tb) to the surface of the sintered magnet body, ) Is diffused into the rare earth sintered magnet body.

Description

RFFE-based rare earth sintered magnet and manufacturing method thereof

The present invention relates to an R-Fe-B-based rare earth sintered magnet having a R ₂ Fe ₁₄ B type compound crystal grain (R is a rare earth element) as a main phase, and a manufacturing method thereof. An element (RL: light rare earth element) (at least one of Nd and Pr) as a main rare earth element (R), and a part of the light rare earth element (RL) is a heavy rare earth element (RH: heavy). The present invention relates to an R-Fe-B rare earth sintered magnet substituted with a rare earth element (at least one selected from the group consisting of Dy, Ho, and Tb), and a manufacturing method thereof.

R-Fe-B rare earth sintered magnets based on Nd ₂ Fe ₁₄ B-type compounds are known as the highest performing magnets among permanent magnets. Voice coil motors (VCMs) and hybrid vehicles of hard disk drives It is used in various motors such as mounting motors and home appliances. When the R-Fe-B-based rare earth sintered magnet is used in various devices such as a motor, it is required to have excellent heat resistance and high coercive force properties in order to cope with the use environment at high temperatures.

As a means of improving the coercive force of the R-Fe-B rare earth sintered magnet, an alloy in which heavy rare earth element (RH) is mixed as a raw material and solvent is used. According to this method, since the rare earth element R of R ₂ Fe ₁₄ B which contains the light rare earth element (RL) as the rare earth element R is replaced with the heavy rare earth element (RH), the crystal of the R ₂ Fe ₁₄ B phase Magnetic anisotropy (an essential physical quantity that determines coercive force) is improved. However, the magnetic moment of the light rare earth element (RL) in the R ₂ Fe ₁₄ B phase is in the same direction as the magnetic moment of Fe, whereas the magnetic moment of the heavy rare earth element (RH) is in the opposite direction to the magnetic moment of Fe. The residual magnetic flux density (B _r ) decreases as the light rare earth element (RL) is replaced with the heavy rare earth element (RH).

On the other hand, heavy rare earth element (RH) is a scarce resource, and therefore the amount of its use is required to be reduced. For this reason, the method of replacing the light rare earth element (RL) entirely with the heavy rare earth element (RH) is not preferable.

In order to express the coercive force improvement effect of the heavy rare earth element (RH) by adding a relatively small amount of the heavy rare earth element (RH), powders such as alloys and compounds containing a lot of the heavy rare earth element (RH) are added to the light rare earth (RL). It is proposed to add to a columnar master alloy powder containing a lot of) and to mold and sinter. According to this method, since the heavy rare earth element (RH) has to be much distributed in the grain boundary vicinity on the R ₂ Fe ₁₄ B, determined on the R ₂ Fe ₁₄ B in the circumferential outer portion (外殼部) effectively improves the magnetic anisotropy It becomes possible. Since the coercive force generating mechanism of the R-Fe-B-based rare earth sintered magnet is a nucleation type, a large amount of heavy rare earth elements (RH) are distributed in the columnar outer portion (near the grain boundaries), thereby increasing the crystal magnetic anisotropy of the whole grain. The nucleation of inverse magnetic spheres is disturbed, and as a result, the coercive force is improved. In addition, since the substitution by the heavy rare earth element (RH) does not occur in the center of the crystal grain which does not contribute to the improvement of the coercive force, the decrease in the residual magnetic flux density (B _r ) can be suppressed.

In practice, however, this method accelerates the diffusion rate of the heavy rare earth element (RH) in the sintering process (which is performed at 1000 to 1200 ° C on an industrial scale), so that the heavy rare earth element (RH) also diffuses to the center of the crystal grain. As a result, it is not easy to obtain the desired tissue structure.

In addition, as another coercive force improvement means of the R-Fe-B-based rare earth sintered magnet, metal, alloy, compound, etc. containing heavy rare earth element (RH) are deposited on the magnet surface in the sintered magnet stage, and then remaining by heat treatment and diffusion. It has been studied to recover or improve the coercive force without significantly reducing the magnetic flux density (Patent Document 1, Patent Document 2 and Patent Document 3).

Patent document 1 contains 1.0 atomic%-50.0 atomic% of at least 1 sort (s) of Ti, W, Pt, Au, Cr, Ni, Cu, Co, Al, Ta, Ag, and remainder R '(R' is Ce, The formation of the alloy thin film layer which consists of at least 1 sort (s) of La, Nd, Pr, Dy, Ho, Tb) in the to-be-grinded surface of a sintered magnet body is disclosed.

Patent document 2 discloses a metal element (R) at a depth equal to or greater than the radius of crystal grains exposed to the outermost surface of a small magnet (where R is a rare earth element selected from Y and Nd, Dy, Pr, Ho, and Tb). (1 or 2 or more types) is disclosed to improve the (BH) max by spreading the modified altered damaged part.

Patent document 3 discloses restoring magnet characteristics by forming a chemical vapor phase growth film mainly composed of rare earth elements on the surface of a magnet having a thickness of 2 mm or less.

Patent document 4 discloses the sorption method of rare earth elements in order to recover the coercive force of an R-Fe-B type micro sintered magnet and powder. In this method, a heat treatment for uniformly heating in vacuum while mixing the sorbed metals (rare earth metals having relatively low boiling points such as Yb, Eu, Sm, etc.) with R-Fe-B-based micro-sintered magnets or powders is performed. . By this heat treatment, the rare earth metal is deposited on the magnet surface and diffuses inside. Patent Document 4 also describes an embodiment in which a rare-earth metal (for example, Dy) having a high boiling point is sorbed. In embodiment using this Dy etc., Dy etc. is selectively heated at high temperature by the high frequency heating method, For example, the boiling point of Dy is 2560 degreeC, and Yb of boiling point 1193 degreeC is heated to 800 degreeC-850 degreeC. It is considered that Dy is heated to a temperature exceeding at least 1000 ° C from the point and the point that it cannot be sufficiently heated by ordinary resistance heating. In addition, it is described that it is preferable to keep the temperature of R-Fe-B type micro sintered magnet and powder at 700 degreeC-850 degreeC.

Patent Document 1: Japanese Patent Laid-Open No. 62-192566

Patent Document 2: Japanese Patent Laid-Open No. 2004-304038

Patent Document 3: Japanese Patent Laid-Open No. 2005-285859

Patent Document 4: Japanese Patent Laid-Open No. 2004-296973

[PROBLEMS TO BE SOLVED BY THE INVENTION]

Since the prior arts disclosed in Patent Document 1, Patent Document 2, and Patent Document 3 all aim to recover the surface of a processed and deteriorated sintered magnet, the diffusion range of the metal element diffused from the surface into the inside is It is limited to the surface vicinity. Therefore, the coercive force improvement effect is hardly obtained with the magnet of thickness 3mm or more.

On the other hand, in the prior art disclosed in Patent Document 4, since a film is formed by heating a rare earth metal such as Dy sufficiently to vaporize, a film formation rate is predominantly faster than the diffusion rate in the magnet, and a thick Dy film is formed on the magnet surface. do. As a result, in the magnet surface layer region (a region from the surface to several tens of micrometers in depth), a large concentration difference of the Dy concentration at the interface between the Dy film and the sintered magnet body is used as a driving force, so that Dy cannot be diffused even in the columnar phase. The residual magnetic flux density B _r decreases.

In addition, in the method of Patent Document 4, since rare earth metals are deposited in portions other than the magnet inside the apparatus (for example, the inner wall of the vacuum chamber) during the film formation process, it is inverse to the resource saving of the heavy rare earth element which is a valuable resource. Done.

In addition, in embodiments targeting low-boiling rare earth metals such as Yb, the coercive force of individual R-Fe-B-based micromagnets is surely recovered, but R-Fe-B-based magnets and sorbed metals are fused or treated during diffusion heat treatment. Since it is difficult to separate from each other afterwards, the remainder of the unreacted sorbent metal (RH) on the surface of the sintered magnet body is virtually unavoidable. This not only reduces the proportion of the magnetic component in the magnet molded body, which leads to a reduction in the magnetic properties, and since the rare earth metal is inherently very active and easily oxidized, the unreacted sorbent metal tends to be a starting point of corrosion in practical environments. not. In addition, since it is necessary to simultaneously perform rotation and vacuum heat treatment for mixing and stirring, a special device in which a rotating mechanism is assembled while maintaining heat resistance and pressure (density) is required. In view of the problem. In addition, when the powder is used as a sorption raw material, safety problems (ignition or harm to the human body) and manufacturing processes become complicated, which increases the cost.

In addition, in the embodiment of the high boiling point rare earth metal including Dy, both the sorption raw material and the magnet are heated by high frequency, so that only the rare earth metal is heated to a sufficient temperature so that the magnet does not affect the magnetic properties. It is not easy to maintain the magnet, and the magnet is limited to a powder state or a very small one which is difficult to induction heating.

The present invention has been made to solve the above problems, and its purpose is to efficiently utilize a small amount of heavy rare earth elements (RH), even if the magnet is relatively thick, heavy rare earth elements (RH) in the outer portion of the columnar crystal grains throughout the magnet It is to provide a R-Fe-B-based rare earth sintered magnet diffused).

MEANS FOR SOLVING THE PROBLEMS [

R-Fe-B-based rare earth sintered magnet manufacturing method according to the present invention, R ₂ Fe ₁₄ B-type compound containing a light rare earth element (RL) (at least one of Nd and Pr) as the main rare earth element (R) Step (a) of preparing an R-Fe-B rare earth sintered magnet body having crystal grains as a main phase, and heavy rare earth elements (RH) (at least one selected from the group consisting of Dy, Ho and Tb) (B) arranging the containing bulk body together with the R-Fe-B-based rare earth sintered magnet body in the process chamber, and the bulk body and the R-Fe-B-based rare earth sintered magnet body between 700 ° C and 1000 ° C. The heavy rare earth element (RH) is supplied to the R-Fe-B based rare earth sintered magnet body while the heavy rare earth element (RH) is supplied from the bulk to the surface of the R-Fe-B based rare earth sintered magnet body. It includes the step (c) to diffuse into the interior.

In a preferred embodiment, in the step (c), the bulk body and the R-Fe-B rare earth sintered magnet body are disposed in the processing chamber without contact, and the average interval is 0.1 mm or more and 300 mm or less. Set within the range.

In a preferred embodiment, in the step (c), the temperature difference between the temperature of the R-Fe-B rare earth sintered magnet body and the bulk body temperature is within 20 ° C.

In a preferred embodiment, in the step (c), the pressure of the atmosphere gas in the processing chamber is adjusted within the range of 10 ^-5 Pa to 500 Pa.

In preferable embodiment, in the said process (c), the temperature of the said bulk body and the said R-Fe-B system rare earth sintered magnet body is hold | maintained for 10 to 600 minutes within the range of 700 degreeC or more and 1000 degrees C or less.

In a preferred embodiment, the sintered magnet body contains 0.1% by mass or more and 5.0% by mass or less of heavy rare earth element (RH) (at least one selected from the group consisting of Dy, Ho, and Tb).

In a preferred embodiment, the sintered magnet body has a content of heavy rare earth element (RH) of 1.5% by mass or more and 3.5% by mass or less.

In a preferred embodiment, the bulk is at least one selected from the group consisting of heavy rare earth elements (RH) and elements X (Nd, Pr, La, Ce, Al, Zn, Sn, Cu, Co, Fe, Ag and In). Species) alloys.

In a preferred embodiment, the element X is Nd and / or Pr.

In a preferred embodiment, after the step (c), a step of applying an additional heat treatment to the R-Fe-B-based rare earth sintered magnet body is included.

Another R-Fe-B-based rare earth sintered magnet manufacturing method according to the present invention is an R-Fe-B system containing light rare earth element (RL) (at least one of Nd and Pr) as the main rare earth element (R). (A) arranging a molded object of the rare earth magnet powder in a processing chamber by opposing a bulk body containing a heavy rare earth element (RH) (at least one selected from the group consisting of Dy, Ho and Tb) and sintering in the processing chamber. (B) to produce a R-Fe-B rare earth sintered magnet body having a R ₂ Fe ₁₄ B compound crystal grain as a main phase by performing the above step; and the bulk body and the R-Fe-B rare earth in the processing chamber. By heating the sintered magnet body, the heavy rare earth element (RH) is supplied to the surface of the R-Fe-B-based rare earth sintered magnet body from the bulk body while the heavy rare earth element (RH) is supplied to the R-Fe-B-based rare earth. The process (C) which diffuses into a sintered magnet body is included.

In a preferred embodiment, the step (B) is sintered for 30 minutes to 600 minutes with a vacuum degree in the processing chamber of 1 Pa to 10 ⁵ Pa and an ambient temperature of 1000 ° C to 1200 ° C in the processing chamber.

In preferable embodiment, the said process (C) heat-process for 10 minutes-600 minutes, with the vacuum degree in the said processing chamber as 1x10 <^-5> Pa-1Pa, and the atmospheric temperature in the said processing chamber as 800 degreeC-950 degreeC.

In a preferable embodiment, after the said process (B), after the atmospheric temperature in a said process chamber reaches 950 degreeC or less, the process (B ') of adjusting the vacuum degree in the said process chamber to 1 * 10 <^-5> Pa ~ 1Pa is included. .

In a preferred embodiment, after the step (B), heat treatment is performed for 30 minutes to 300 minutes with the vacuum degree in the processing chamber of 1 × 10 ^-5 Pa to 1Pa and the atmospheric temperature of the processing chamber to 1000 ° C to 1200 ° C, Thereafter, the method further includes a step (B ″) of setting the ambient temperature in the processing chamber to 950 ° C. or less.

The R-Fe-B-based rare earth sintered magnet according to the present invention is manufactured by any of the above-described manufacturing methods, and contains light rare earth element (RL) (at least one of Nd and Pr) as the main rare earth element (R). An R-Fe-B rare earth sintered magnet having a R ₂ Fe ₁₄ B type crystal grain as a main phase, and selected from the group consisting of heavy rare earth elements (RH) (Dy, Ho and Tb) introduced into the surface by grain boundary diffusion. And a concentration of heavy rare earth elements (RH) in the central portion of the R ₂ Fe ₁₄ B-type compound crystal grain in the surface layer region from the surface to a depth of 100 μm, and the R ₂ Fe ₁₄ B A difference of 1 atomic% or more occurs between heavy rare earth element (RH) concentrations in the grain boundary phase of the type compound crystal grains.

EFFECTS OF THE INVENTION [

In the present invention, by performing grain boundary diffusion of the heavy rare earth element (RH) (at least one selected from the group consisting of Dy, Ho and Tb), the heavy rare earth element (RH) is supplied to a deep position inside the sintered magnet body, The light rare earth element (RL) can be efficiently replaced with the heavy rare earth element (RH) at the columnar outer portion. As a result, it becomes possible to raise coercive force H _cJ while suppressing the fall of residual magnetic flux density B _r .

BRIEF DESCRIPTION OF THE DRAWINGS The example of the structure of the processing container used suitably for the manufacturing method of the R-Fe-B system rare earth sintered magnet which concerns on this invention, and the example of the arrangement relationship of the RH bulk body and the sintered magnet body in a processing container are typical. It is sectional drawing shown.

It is a graph which shows the time change of the atmospheric temperature and atmospheric gas pressure in a process chamber in the sintering and diffusion process of this invention. The dashed-dotted line in a graph has shown atmospheric gas pressure, and the solid line has shown atmospheric temperature.

It is a graph which shows the other time change of the atmospheric temperature and atmospheric gas pressure in a process chamber in the sintering and diffusion process of this invention. The dashed-dotted line in a graph has shown atmospheric gas pressure, and the solid line has shown atmospheric temperature.

4 is a photograph showing the results of the cross-sectional EPMA analysis obtained for Sample 2, which is an embodiment of the present invention, wherein (a), (b), (c) and (d) are BEI (reflected electron beam image), Nd, Fe and It is a mapping photograph showing the distribution of Dy.

5 is a photograph showing the cross-sectional EPMA analysis results obtained for Sample 4, which is an example of the present invention, wherein (a), (b), (c) and (d) are BEI (reflected electron beam image), Nd, Fe and It is a mapping photograph showing the distribution of Dy.

It is a graph which shows the result of having measured the Dy density | concentration in columnar center part and a grain boundary triple point about the sample 2 and the sample 3 which are Examples of this invention.

It is a graph which shows the result of having measured Dy density | concentration in columnar center part and a grain boundary triple point about the sample 4 and the sample 5 which are the Example of this invention.

FIG. 8A is a graph showing the relationship between the residual magnetic flux density B _r and the treatment temperature, and FIG. 8B is a graph showing the relationship between the coercive force H _cJ and the treatment temperature.

FIG. 9A is a graph showing the relationship between the residual magnetic flux density B _r and the processing time, and FIG. 9B is a graph showing the relationship between the coercive force H _cJ and the processing time.

FIG. 10A is a graph showing the relationship between the residual magnetic flux density B _r and the atmospheric pressure, and FIG. 10B is a graph showing the relationship between the coercive force H _cJ and the atmospheric pressure.

11 is a cross-sectional view showing the arrangement in the Mo-pack used in the embodiment of the present invention.

It is a photograph which shows the external appearance observation result of the Mo pack inner wall after heat processing.

It is sectional drawing which shows the arrangement | positioning in the Mo pack used by the Example of this invention.

It is a figure which shows the arrangement relationship of the Dy board and sintered magnet body in the Example of this invention.

15 is a graph showing the relationship between the distance from the magnet body to the Dy plate and the magnet characteristics.

It is sectional drawing which shows the arrangement relationship of a Dy board and a sintered magnet body.

17 is a graph showing the relationship between the arrangement of the Dy plates and the magnet characteristics.

FIG. 18 is a photograph showing an EPMA analysis result of the surface of the sintered magnet body after heat treatment when the Dy plate is disposed only under the sintered magnet body, and FIG. 18A shows the analysis result at the center of the upper surface of the sintered magnet body. It is a photograph and FIG. 18 (b) is a photograph which shows the analysis result in the center part of the lower surface of a sintered magnet body.

19 is a photograph showing Example 7. FIG.

20 is a cross-sectional view showing the arrangement relationship between the Dy-X alloy plate and the sintered magnet body in the processing container used for the manufacture of Example 8. FIG.

(A), (b), and (c) of FIG. 21 show the residual magnetic flux density (B _r ), the coercive force (H _cJ ), and the square ratio (H), respectively, for the samples of the magnets produced by the manufacturing method of the present invention. _k / H _cJ ).

(A) is a figure which shows the arrangement relationship of a sintered magnet body and a Dy board, and FIG. 22 (b) is a figure which shows the crystal orientation of a sintered magnet body.

FIG. 23A is a graph showing residual magnetic flux density B _r measured for Example 9, and FIG. 23B is a graph showing coercive force H _cJ measured for Example 9. FIG.

24 is a graph showing a relationship between the coercive force H _cJ and the amount of grinding obtained in Example 9. FIG.

25 (a) and 25 (b) are perspective views showing which part of the surface of the sintered magnet body is covered with Nb foil in Example 10. FIG.

(A) is a graph showing a coercive force variation amount (ΔH _cJ) measured with a BH tracer for composition L ~ Composition P, (b) of FIG. 26 in Fig. 26 is a graph showing these in the residual magnetic flux density change (ΔB _r) to be.

(A) is a graph which shows the measured value of the residual magnetic flux density (B _r ) about 12 samples, and FIG. 27 (b) is a graph which shows the measured value of the coercive force (H _cJ ) regarding the sample. to be.

[Description of Symbols]

2… Sintered magnet body

4… RH bulk body

6... Treatment room

8… Nb net

The R-Fe-B-based rare earth sintered magnet of the present invention contains heavy rare earth element (RH) introduced into it by grain boundary diffusion from the surface of the sintered compact. Here, the heavy rare earth element (RH) is at least one kind selected from the group consisting of Dy, Ho and Tb.

The R-Fe-B rare earth sintered magnet of the present invention supplies heavy rare earth elements (RH) from the surface of the sintered body to the inside of the sintered magnet body while supplying the heavy rare earth elements (RH) from the heavy rare earth bulk (RH bulk) to the surface of the sintered magnet body. It is suitably manufactured by diffusing.

In the manufacturing method of this invention, vaporization (sublimation) of RH bulk body is made to grow RH film | membrane by heating the bulk body of the rare rare earth element (RH) and the rare earth sintered magnet body which are hard to vaporize (sublimate) to 700 degreeC or more and 1000 degrees C or less. The heavy rare earth element (RH) that has flown to the surface of the sintered magnet body is rapidly diffused into the magnet body while the speed is suppressed so as not to be extremely faster than the diffusion speed of the RH into the magnet. The temperature range of 700 ° C or more and 1000 ° C or less is a temperature at which vaporization (sublimation) of the heavy rare earth element (RH) hardly occurs, but active diffusion of rare earth elements in the R-Fe-B rare earth sintered magnet occurs. It is also a temperature. Therefore, the heavy rare earth element (RH) that has flown on the surface of the magnet body preferentially promotes the diffusion of grain boundaries into the magnet body rather than forming a film on the surface of the magnet body.

In the present specification, the diffusion of heavy rare earth RH from the surface of the sintered magnet body to the inside while supplying the heavy rare earth RH from the heavy rare earth bulk body (RH bulk body) to the surface of the sintered magnet body is referred to simply as 'deposition and diffusion'. There is a case. According to the present invention, the heavy rare earth element (RH) diffuses and penetrates into the magnet at a speed higher than the rate (rate) at which the rare earth element (RH) diffuses into the main phase located near the surface of the sintered magnet body. I will go.

Conventionally, it has been thought that heating to a high temperature of more than 1000 ° C. is required for vaporization (sublimation) of heavy rare earth elements (RH) such as Dy, and it is unreasonable to deposit Dy on the surface of the magnet body when heating is 700 ° C. or more and 1000 ° C. or less. I thought. However, according to the experiments of the present inventors, it can be seen that contrary to the conventional prediction, it is possible to supply and diffuse the heavy rare earth element (RH) to the rare earth magnets arranged oppositely even at 700 ° C or more and 1000 ° C or less.

In the conventional technique in which a heavy rare earth element (RH) film (RH film) is formed on the surface of a sintered magnet body and then diffused into the sintered magnet body by heat treatment, 'diffusion in particles' is formed in the surface layer region in contact with the RH film. It progresses remarkably and the magnet characteristic deteriorates. In contrast, the present invention maintains the temperature of the sintered magnet body at a level suitable for diffusion while supplying the heavy rare earth element (RH) to the surface of the sintered magnet body while keeping the growth rate of the RH film low. The heavy rare earth element (RH) that has flown quickly penetrates into the sintered magnet body by grain boundary diffusion. Therefore, in the surface layer region, 'grain diffusion' occurs more preferentially than 'in-particle diffusion', so that it is possible to suppress a decrease in the residual magnetic flux density B _r and to effectively improve the coercive force H _cJ .

Since the coercive force generating mechanism of the R-Fe-B-based rare earth sintered magnet is a nucleation type, when the crystal magnetic anisotropy in the columnar outer portion increases, the nucleation of the inverted sphere is suppressed in the vicinity of the grain boundary phase in the columnar phase. The coercive force of H _cJ is effectively improved. In the present invention, since the heavy rare earth substitution layer can be formed in the columnar outer portion not only in the region close to the surface of the sintered magnet body but also in the region far from the magnet surface, the crystal magnetic anisotropy is increased throughout the magnet, and the coercive force (H) of the whole magnet is increased. _cJ ) is sufficiently improved. Therefore, according to the present invention, even if the amount of heavy rare earth elements (RH) consumed is small, it is possible to diffuse and penetrate the heavy rare earth elements (RH) to the inside of the sintered body, and efficiently the heavy rare earth elements (RH) in the columnar outer portion. By forming the concentrated layer), it becomes possible to improve the coercive force (H _cJ ) while suppressing the decrease in the residual magnetic flux density (B _r ).

As the heavy rare earth element (RH) to be replaced with the light rare earth element (RL) in the columnar outer portion, Dy is most preferable in consideration of the easiness of deposition and diffusion, cost, and the like. However, since the crystal magnetic anisotropy of Tb ₂ Fe ₁₄ B is higher than the crystal magnetic anisotropy of Dy ₂ Fe ₁₄ B and about three times the crystal magnetic anisotropy of Nd ₂ Fe ₁₄ B, when Tb is deposited and diffused, the sintered magnet The improvement of coercive force can be realized most efficiently without reducing the residual low speed density of the sieve. When using Tb, it is preferable to carry out vapor deposition and diffusion at high temperature and high vacuum degree than when using Dy.

As can be seen from the above description, in the present invention, the heavy rare earth element (RH) is not necessarily added in the raw material alloying step. That is, a known R-Fe-B rare earth sintered magnet containing light rare earth element RL (at least one of Nd and Pr) as rare earth element R is prepared, and the heavy rare earth element RH is formed from the surface thereof. Diffuse into the magnet. When only the conventional rare earth layer is formed on the surface of the magnet, it is difficult to diffuse the heavy rare earth element (RH) to the depth inside the magnet even if the diffusion temperature is increased. This makes it possible to efficiently supply the heavy rare earth element (RH) to the outer portion of the columnar phase located inside the sintered magnet body. Of course, you may apply this invention to the R-Fe-B type sintered magnet to which heavy rare earth element (RH) is added in the raw material alloying step. However, when a large amount of heavy rare earth element (RH) is added in the raw material alloying step, the effect of the present invention cannot be sufficiently exhibited, so that a relatively small amount of heavy rare earth element (RH) can be added.

Next, the preferable example of the diffusion process which concerns on this invention is demonstrated, referring FIG. 1 shows an arrangement example of the sintered magnet body 2 and the RH bulk body 4. In the example shown in FIG. 1, the sintered magnet body 2 and the RH bulk body 4 are mutually arrange | positioned at predetermined intervals in the process chamber 6 which consists of a high melting point metal material. The process chamber 6 of FIG. 1 is equipped with the member holding the some sintered magnet body 2, and the member holding the RH bulk body 4. As shown in FIG. In the example of FIG. 1, the sintered magnet body 2 and the upper RH bulk body 4 are hold | maintained by the net 8 made from Nb. The configuration holding the sintered magnet body 2 and the RH bulk body 4 is not limited to the above examples and is arbitrary. However, the structure which cuts off between the sintered magnet body 2 and the RH bulk body 4 should not be employ | adopted. In the present invention, the term “facing” means that the sintered magnet body and the RH bulk body face each other without being interrupted. In addition, "facing arrangement" does not require arrange | positioning so that main surfaces may become parallel.

The temperature of the processing chamber 6 is raised by heating the processing chamber 6 with a heating device (not shown). At this time, the temperature of the processing chamber 6 is adjusted, for example, in the range of 700 ° C to 1000 ° C, preferably 850 ° C to 950 ° C. In this temperature range, the vapor pressure of the heavy rare earth metal (RH) is low and hardly vaporizes. According to the conventional common knowledge, it was considered that in such a temperature range, heavy rare earth elements RH evaporated from the RH bulk body 4 cannot be supplied to the surface of the sintered magnet body 2 to form a film.

However, the present inventors place the sintered magnet body 2 and the RH bulk body 4 in close proximity without contacting each other, so that the surface of the sintered magnet body 2 is several 탆 (for example, 0.5 탆 / Hr ~). It is possible to precipitate heavy rare earth metals at a low rate of 5 µm / Hr), and also by adjusting the temperature of the sintered magnet body 2 to an appropriate temperature range equal to or higher than that of the RH bulk body 4, It was found that heavy rare earth metal (RH) precipitated from (氣相) can be deeply diffused into the sintered magnet body 2 as it is. This temperature range is a preferable temperature range in which the RH metal diffuses inside through the grain boundary phase of the sintered magnet body 2, and the slow precipitation of the RH metal and the rapid diffusion into the inside of the magnet body are performed efficiently.

In the present invention, since the minutely vaporized RH is precipitated on the surface of the sintered magnet body at a low rate, the inside of the processing chamber is heated to a high temperature of more than 1000 ° C. like the deposition of RH by conventional vapor phase film formation, or the sintered magnet There is no need to add voltage to the sieve or the RH bulk sieve.

In the present invention, as described above, the heavy rare earth element (RH) that has flown to the surface of the sintered magnet body is rapidly diffused into the magnet body while suppressing vaporization and sublimation of the RH bulk body. For this purpose, it is preferable to set the temperature of RH bulk body in the range of 700 degreeC or more and 1000 degrees C or less, and to set the temperature of a sintered magnet body in the range of 700 degreeC or more and 1000 degrees C or less.

The distance between the sintered magnet body 2 and the RH bulk body 4 is set to 0.1 mm to 300 mm. It is preferable that this interval is 1 mm or more and 50 mm or less, It is more preferable that it is 20 mm or less, It is still more preferable that it is lOmm or less. If it is possible to maintain the state spaced at such a distance, the arrangement relationship of the sintered magnet body 2 and the RH bulk body 4 may be a top, left, or a relatively moving arrangement. However, it is preferable that the distance between the sintered magnet body 2 and the RH bulk body 4 during vapor deposition and diffusion treatment does not change. For example, the form which accommodates a sintered magnet body in a rotating barrel and processes it with stirring is not preferable. In addition, since vaporized RH forms a uniform RH atmosphere in the distance range mentioned above, the area of the surface which opposes does not care, and the surface of the narrowest area of each other may oppose. According to the inventor's examination, when the RH bulk body is provided perpendicular to the magnetization direction (c-axis direction) of the sintered magnet body 2, it is found that RH diffuses most efficiently into the sintered magnet body 2. there was. This is considered to be because when RH diffuses inward through the grain boundary phase of the sintered magnet body 2, the diffusion speed in the magnetization direction is faster than the diffusion speed in the vertical direction. The reason why the diffusion speed in the magnetization direction is faster than that in the vertical direction is presumably due to the difference in anisotropy according to the crystal structure.

In the conventional vapor deposition apparatus, since the mechanism around the vapor deposition material supply portion is obstructed or it is necessary to irradiate electron beams or ions to the vapor deposition material supply portion, it is necessary to provide a considerable distance between the vapor deposition material supply portion and the workpiece. there was. For this reason, the vapor deposition material supply part (RH bulk body 4) has not been arrange | positioned adjacent to to-be-processed object (sintered magnet body 2) like this invention. As a result, it was considered that the vapor deposition material could not be sufficiently supplied onto the object, unless the vapor deposition material was heated to a sufficiently high temperature and sufficiently vaporized.

In contrast, in the present invention, no special mechanism for vaporizing (sublimation) the vapor deposition material is required, and the RH metal can be deposited on the magnet surface by controlling the temperature of the entire processing chamber. In addition, the "process chamber" in this specification includes the space which arrange | positioned the sintered magnet body 2 and the RH bulk body 4 widely, and it may mean the process chamber of a heat processing furnace, and is accommodated in such a process chamber. It may also mean a processing container.

In addition, in the present invention, the amount of vaporization of the RH metal is small, but since the sintered magnet body and the RH bulk body 4 are arranged at a non-contact or close distance, the vaporized RH metal is efficiently precipitated on the surface of the sintered magnet body, thereby It is hard to be attached to a wall surface. If the wall surface in the processing chamber is made of a material that does not react with RH, such as a heat-resistant alloy such as Nb or ceramics, the RH metal attached to the wall is vaporized again and finally precipitated on the surface of the sintered magnet body. Therefore, unnecessary consumption of heavy rare earth element (RH) which is a valuable resource can be suppressed.

In the treatment temperature range of the diffusion process performed in the present invention, the RH bulk body does not melt or soften, and since the RH metal is vaporized (sublimed) from the surface, a large change does not occur in the appearance shape of the RH bulk body in one treatment step. It is not possible to use repeatedly.

Further, since the RH bulk body and the sintered magnet body are disposed in close proximity, the amount of the sintered magnet body that can be mounted in the processing chamber having the same volume increases, and the loading efficiency is high. In addition, since a large-scale device is not required, a general vacuum heat treatment furnace can be utilized, which makes it possible to avoid an increase in manufacturing cost and is practical.

It is preferable that the process chamber at the time of heat processing is an inert atmosphere. "Inert atmosphere" in this specification shall include the state filled with vacuum or an inert gas. In addition, the 'inert gas' may be included in the 'inert gas' as long as it is a rare gas such as argon (Ar), but does not chemically react between the RH bulk body and the sintered magnet body. The pressure of the inert gas is reduced to show a value lower than atmospheric pressure. If the atmospheric pressure in the processing chamber is close to atmospheric pressure, it becomes difficult for the RH metal to be supplied from the RH bulk body to the surface of the sintered magnet body, but the diffusion amount is controlled by the diffusion rate from the magnet surface to the inside, so the atmospheric pressure in the processing chamber is, for example, 10 ² Pa or less is sufficient, and even if the atmospheric pressure in the processing chamber is further reduced, the diffusion amount (improved coercive force) of the RH metal is not significantly affected. The diffusion amount is more sensitive to the temperature of the sintered magnet than the pressure.

The RH metal that has been blown onto the surface of the sintered magnet body and diffuses into the grain boundary phase toward the inside of the magnet by using the difference between the heat of the atmosphere and the RH concentration at the magnet interface as the driving force. At this time, part of the light rare earth element (RL) in the R ₂ Fe ₁₄ B phase is replaced by the heavy rare earth element (RH) diffused and infiltrated from the magnet surface. As a result, a layer in which the heavy rare earth element (RH) is concentrated is formed in the outer portion of the R ₂ Fe ₁₄ B phase.

By the formation of such an RH concentrated layer, the crystal magnetic anisotropy of the columnar outer portion becomes high, and the coercive force H _cJ is improved. In other words, the use of a small amount of RH metal diffuses and penetrates the heavy rare earth element (RH) to the depth of the inside of the magnet to form an RH concentrated layer efficiently in the columnar outer portion, thereby reducing the residual magnetic flux density (B _r ). It is possible to improve the coercive force H _cJ throughout the magnet while suppressing it.

According to the prior art, the rate (diffusion rate) at which the heavy rare earth element (RH) such as Dy is deposited on the surface of the sintered magnet body (growth rate of the film) is diffused into the sintered magnet body (diffusion rate) and It was significantly higher in comparison. For this reason, after forming the RH film of several micrometers or more in thickness on the surface of a sintered magnet body, heavy rare earth element (RH) diffused in the inside of the sintered magnet body from this RH film. The heavy rare earth element (RH) supplied from the solid-state RH film not in the gaseous phase not only diffuses grain boundaries but also diffuses into particles inside the main phase located in the surface layer region of the sintered magnet body, thereby lowering the residual magnetic flux density (B _r ). Caused. The region in which the heavy rare earth element (RH) diffuses into the particles within the main phase and there is no difference in the RH concentration between the main phase and the grain boundary phase is limited to the surface layer region (for example, 100 µm or less in thickness) of the sintered magnet body. When the thickness of the whole magnet is thin, the fall of the residual magnetic flux density B _r cannot be avoided.

According to the present invention, however, heavy rare earth elements (RH) such as Dy supplied in the gas phase collide with the surface of the sintered magnet body, and then quickly diffuse into the sintered magnet body. This means that the heavy rare earth element RH penetrates deeply into the sintered magnet body through the grain boundary phase at a faster diffusion rate before it diffuses into the main phase located in the surface layer region.

According to the present invention, in the surface layer region from the surface of the sintered magnet body to a depth of 100 µm, the concentration of the heavy rare earth element (RH) in the central portion of the R ₂ Fe ₁₄ B type crystal grains, and the R ₂ Fe ₁₄ B type compound A difference of 1 atomic% or more occurs between the concentrations of the heavy rare earth elements (RH) in the grain boundaries of the grains. In order to suppress the fall of the residual magnetic flux density (B _r ), it is preferable to form a concentration difference of 2 atomic%.

In addition, it is preferable to set content of RH which diffuses in the range of 0.05% or more and 1.5% or less by the weight ratio of the whole magnet. It is because when it exceeds 1.5%, the fall of residual magnetic flux density (B _r ) may not be suppressed, and when less than 0.1%, the improvement effect of coercive force (H _cJ ) is small. By heat-treating 10 minutes-180 minutes in said temperature range and pressure, the diffusion amount of 0.1%-1% can be achieved. The treatment time means the time when the temperature of the RH bulk body and the sintered magnet body is 700 ° C or more and 1000 ° C or less and the pressure is 10 ^-5 Pa or more and 500Pa or less, and only showing the time that is kept constant at a specific temperature and pressure. no.

It is preferable that the surface state of the sintered magnet is closer to the metal state so that RH easily diffuses and penetrates, and it is preferable to perform activation treatment such as acid washing or blasting in advance. However, in the present invention, when heavy rare earth element (RH) is vaporized and deposited on the surface of the sintered magnet body in an active state, it diffuses into the sintered magnet body at a higher speed than forming a solid layer. Therefore, the surface of a sintered magnet body may be in the state in which oxidation progressed after the sintering process or the cutting process is completed, for example.

According to the present invention, since it is possible to diffuse the heavy rare earth element (RH) mainly through the grain boundary phase, it is possible to efficiently diffuse the heavy rare earth element (RH) to a deeper position inside the magnet by controlling the treatment time. .

In addition, since the evaporation rate of the heavy rare earth element (RH) can be controlled by adjusting the pressure of the processing atmosphere, for example, the RH bulk body is disposed in the apparatus beforehand during the sintering step, Therefore, it is also possible to perform a sintering reaction, suppressing evaporation of RH under high atmospheric gas pressure. In this case, after completion of sintering, the atmospheric gas pressure is lowered to perform evaporation and diffusion of RH, so that the sintering step and the coercive force improving step can be performed continuously using the same equipment. This method is described in detail in the second embodiment.

The shape and size of the RH bulk body are not particularly limited, and may be plate-shaped or indeterminate (gravel). Many micro holes (diameter of about 10 micrometers in diameter) may exist in RH bulk body. The RH bulk body is preferably formed of an RH metal containing at least one heavy rare earth element (RH) or an alloy containing RH. In addition, the higher the vapor pressure of the material of the RH bulk body, the larger the amount of RH introduced per unit time, which is more efficient. Oxides, fluorides, nitrides, and the like containing heavy rare earth elements (RH) have extremely low vapor pressures, so that deposition and diffusion hardly occur within this condition range (temperature, vacuum degree). Therefore, even if the RH bulk body is formed from oxides, fluorides, nitrides, etc. containing heavy rare earth elements (RH), the coercive force improvement effect is not obtained.

According to the present invention, even for thick magnets having a thickness of 3 mm or more, both the residual magnetic flux density (B _r ) and the coercive force (H _cJ ) are increased by using a small amount of heavy rare earth elements (RH), and magnetic properties are improved even at high temperatures. A high performance magnet that does not degrade can be provided. Such a high performance magnet greatly contributes to the realization of a very small and high power motor. The effect of the present invention using grain boundary diffusion is particularly remarkable in magnets having a thickness of 10 mm or less.

In the present invention, the heavy rare earth element (RH) may be diffused and penetrated from the entire surface of the sintered magnet body, or the heavy rare earth element (RH) may be diffused and penetrated from a part of the surface of the sintered magnet body. In order to diffuse and penetrate RH from a part of the surface of the sintered magnet body, for example, masking a portion of the sintered magnet body that is not intended to diffuse and penetrate RH may be performed in the same manner as described above. . According to this method, it is possible to obtain a magnet in which the coercive force H _cJ is partially improved.

If further heat treatment is performed on the magnet which has undergone the deposition and diffusion process of the present invention, the coercive force (H _cJ ) can be further improved. The conditions (processing temperature, time) of an additional heat processing should just be conditions similar to vapor deposition and diffusion conditions, and it is preferable to hold | maintain 10 minutes-600 minutes at the temperature of 700 degreeC-1000 degreeC.

The additional heat treatment may be performed as it is without the heavy rare earth element (RH) being evaporated by raising the Ar partial pressure after completion of the diffusion process to about 10 ³ Pa. You may only perform heat processing on the conditions similar to a process.

Since mechanical strength, such as break strength in a sintered magnet body, improves by vapor deposition and diffusion, it is preferable practically. This results in improved crystal coherence of the main phase and the grain boundary phase as the distortion inherent in the sintered magnet body during the deposition and diffusion occurs, the processing deterioration layer is recovered, or the heavy rare earth element (RH) diffuses. Guess as. When the crystal coherence of columnar and grain boundary phases is improved, the grain boundaries are strengthened and the resistance to grain breakage is improved.

EMBODIMENT OF THE INVENTION Hereinafter, preferable embodiment of the method of manufacturing the R-Fe-B type rare earth sintered magnet which concerns on this invention is described.

(Embodiment 1)

[Raw alloy]

First, an alloy containing light rare earth element (RL) of 25% by mass or more and 40% by mass or less, 0.6% by mass to 1.6% by mass of B (boron), balance Fe and unavoidable impurities is prepared. A part of B may be substituted with C (carbon), and a part of Fe (50 atomic% or less) may be substituted with another transition metal element (for example, Co or Ni). This alloy consists of Al, Si, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, In, Sn, Hf, Ta, W, Pb and Bi according to various purposes It may contain 0.01 mass%-about 1.0 mass% of at least 1 sort (s) of additional element M chosen from the group.

The alloy can be suitably produced by quenching the molten metal of the raw material alloy, for example, by a strip casting method. Hereinafter, the preparation of the quench solidification alloy according to the strip cast method will be described.

First, the raw material alloy having the above composition is melted by high frequency melting in an argon atmosphere to form a molten metal of the raw material alloy. Subsequently, after maintaining this molten metal about 1350 degreeC, it is quenched by the single roll method and the flake-shaped alloy ingot of about 0.3 mm in thickness is obtained, for example. The alloy slabs thus produced are pulverized, for example, into flakes having a size of 1 mm to 10 mm before the next hydrogen pulverization. On the other hand, a method for producing a raw material alloy by the strip casting method is disclosed in, for example, US Patent No. 5,383,978.

[Coarse pulverization process]

The alloy slabs roughly crushed into the above flakes are accommodated in the hydrogen furnace. Subsequently, a hydrogen embrittlement treatment (hereinafter also referred to as "hydrogen crushing treatment") is performed inside the hydrogen. When taking out coarse grinding alloy powder after hydrogen grinding from a hydrogen furnace, it is preferable to perform taking out operation in inert atmosphere so that coarse grinding powder may not contact with air | atmosphere. This is because the coarsely pulverized powder can be prevented from being oxidized and generated, and the deterioration of the magnetic properties of the magnet can be suppressed.

The rare earth alloy is pulverized to a size of about 0.1 mm to several mm by hydrogen pulverization, and the average particle diameter thereof becomes 500 탆 or less. It is preferable to cool | pulverize while cooling a raw material alloy embrittled after hydrogen grinding finely. What is necessary is just to lengthen a cooling process time relatively, when taking out a raw material in the comparatively high temperature state.

[Fine pulverization process]

Subsequently, the coarsely pulverized powder is pulverized using a jet mill grinding device. The cyclone classifier is connected to the jet mill grinder used by this embodiment. The jet mill crusher receives a rare earth alloy (coarse pulverized powder) roughly crushed in the coarse pulverization process and pulverizes it in the pulverizer. The powder ground in the mill is collected in a recovery tank via a cyclone classifier. In this way, fine powders of about 0.1 μm to 20 μm (typically 3 μm to 5 μm) can be obtained. The grinding device used for such pulverization is not limited to a jet mill, but may be an attritor or a ball mill. A lubricating agent such as zinc stearate may be used as a grinding aid during grinding.

[Press molding]

In the present embodiment, for example, 0.3 wt% of a lubricant is added and mixed with the magnetic powder produced by the above method in a locking mixer, and the surface of the alloy powder particles is coated with the lubricant. Next, the magnetic powder produced by the above-described method is molded in an oriented magnetic field using a known press apparatus. The intensity of the magnetic field to be applied is, for example, 1.5 tesla to 1.7 tesla (T). In addition, the molding pressure is set such that the green density of the molded body is, for example, about 4 g / cm 3 to 4.5 g / cm 3.

[Sintering process]

For the powder compact, the step of holding at a temperature within the range of 650 ° C to 1000 ° C for 10 minutes to 240 minutes, and then sintering at a temperature higher than the holding temperature (for example, 1000 ° C to 1200 ° C). It is preferable to perform the process which advances sequentially. During sintering, especially when a liquid phase is produced (temperature is in the range of 650 ° C. to 1000 ° C.), the R rich phase in the grain boundary phase begins to melt and a liquid phase is formed. Then, sintering advances and a sintered magnet body is formed. As described above, since the deposition and diffusion treatment can be applied even in the state where the surface of the sintered magnet body is oxidized, the aging treatment (400 ° C. to 700 ° C.) and the grinding for dimension adjustment may be performed.

[Deposition and diffusion process]

Subsequently, the heavy rare earth element (RH) is diffused and penetrated efficiently into the thus produced sintered magnet body to improve the coercive force (H _cJ ). Specifically, the RH bulk body containing the heavy rare earth element (RH) and the sintered magnet body are disposed in the processing chamber shown in FIG. 1, and the heavy rare earth element RH is supplied from the RH bulk body to the surface of the sintered magnet body by heating. While spreading inside the sintered magnet body.

In the diffusion process in the present embodiment, the temperature of the sintered magnet body is preferably equal to or larger than the bulk body temperature. Here, that the temperature of a sintered magnet body is equal to the temperature of a bulk body shall mean that the temperature difference of both is within 20 degreeC. Specifically, it is preferable to set the temperature of the RH bulk body within the range of 700 ° C. or higher and 1000 ° C. or lower, and further set the temperature of the sintered magnet body within the range of 700 ° C. or higher and 1000 ° C. or lower. In addition, the space | interval of a sintered magnet body and a RH bulk body is set to 0.1 mm-300 mm, Preferably it is 3 mm-10 mm, More preferably, 4 mm-50 mm.

Further, the deposition and diffusion process, the pressure of the atmospheric gas at the time was 10 ^-5 Pa ~ 500Pa If done properly the vaporization (sublimation) of the RH bulk body, vapor deposition, it is possible to perform spreading processing. In order to perform vapor deposition and diffusion treatment efficiently, it is preferable to set the pressure of the atmospheric gas within the range of 10 ^-3 Pa to 1 Pa. Moreover, it is preferable that the time which keeps the temperature of RH bulk body and a sintered magnet body in the range of 700 degreeC or more and 100 degrees C or less is set to 10 minutes-600 minutes. However, the holding time means a time when the temperature of the RH bulk body and the sintered magnet body is 700 ° C. or more and 100 ° C. or less, and the pressure is 10 ⁻⁵ Pa or more and 500 Pa or less. It does not indicate.

The diffusion process in the present embodiment is not sensitive to the surface condition of the sintered magnet body, and a film made of Al, Zn or Sn may be formed on the surface of the sintered magnet body before the diffusion process. This is because Al, Zn and Sn are low melting point metals, and small amounts do not deteriorate the magnetic properties and do not hinder the diffusion. On the other hand, the bulk body does not have to be composed of one type of element, but the heavy rare earth element (RH) and the element X (Nd, Pr, La, Ce, Al, Zn, Sn, Cu, Co, Fe, Ag and In Or an alloy of at least one selected from the group consisting of: a. Since the element X lowers the melting point of the grain boundary, it can be expected to have an effect of promoting the grain boundary diffusion of the heavy rare earth element (RH). By vacuum heat treatment in such a state that the bulk body of the alloy and the Nd sintered magnet are spaced apart from each other, the heavy rare earth element (RH) and the element X are deposited on the magnet surface and preferentially become a liquid phase grain phase (Nd rich phase). Can be diffused into the magnet.

In addition, since a small amount of Nd and Pr in the grain boundary is vaporized during the heat treatment for diffusion, when element X is Nd and / or Pr, evaporated Nd and / or Pr is preferable because it can be replenished.

After the diffusion treatment, the above-described additional heat treatment (700 ° C. to 1000 ° C.) may be performed. In addition, although an aging process (400 degreeC-700 degreeC) is performed as needed, when performing further heat processing (700 degreeC-1000 degreeC), it is preferable to perform an aging process after that. Further heat treatment and aging treatment may be performed in the same treatment chamber.

In practical use, it is preferable to apply a surface treatment to the sintered magnet body after vapor deposition and diffusion. Surface treatment should just be a well-known surface treatment, For example, surface treatment, such as Al vapor deposition, electro Ni plating, resin coating, etc., can be performed. Prior to the surface treatment, known pretreatment such as sand blast treatment, barrel treatment, etching treatment, and mechanical grinding may be performed. Moreover, you may grind for dimensional adjustment after a diffusion process. Through this process, the coercive force improvement effect is almost unchanged. The grinding amount for dimensional adjustment is 1 micrometer-300 micrometers, More preferably, it is 5-100 micrometers, More preferably, it is 10-30 micrometers.

(Embodiment 2)

In this embodiment, first, a rare earth element of 25% by mass or more and 40% by mass or less (of which heavy rare earth element (RH) is 0.1% by mass or more and 5.0% by mass or less, and the remainder is light rare earth element (RL)) and 0.6 mass An alloy containing not less than% and 1.6% by mass of B (boron) and the balance Fe and unavoidable impurities is prepared. A part of B may be substituted with C (carbon), and a part of Fe (50 atomic% or less) may be substituted with another transition metal element (for example, Co or Ni). This alloy consists of Al, Si, Ti, V, Cr, Mn, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Ag, In, Sn, Hf, Ta, W, Pb and Bi according to various purposes It may contain 0.01 mass%-about 1.0 mass% of at least 1 sort (s) of additional element M chosen from the group.

Thus, in this embodiment, 0.1 mass% or more and 5.0 mass% or less of heavy rare earth elements (RH) are added to a raw material alloy. That is, the well-known R-Fe-B type | system | group which contains light rare earth element (RL) (at least 1 sort (s of Nd and Pr)) and 0.1 mass% or more and 5.0 mass% or less of the heavy rare earth element (RH) as a rare earth element (R). After preparing the rare earth sintered magnet, heavy rare earth element (RH) is diffused from the surface into the magnet by vapor deposition and diffusion again.

In the present embodiment, the R-Fe-B-based rare earth sintered magnet body before vapor deposition and diffusion is mainly composed of R ₂ Fe ₁₄ B type compound phase crystal grains containing light rare earth element (RL) as the main rare earth element (R). Furthermore, 0.1 mass% or more and 5.0 mass% or less of heavy rare earth elements (RH) are contained. Since the heavy rare earth element (RH) exists in both phases of the main phase and the grain boundary phase, the heavy rare earth element (RH) is present on the surface of the sintered magnet body during deposition and diffusion as compared with the case where the heavy rare earth element (RH) is not added to the raw material alloy. The difference in concentration of heavy rare earth elements (RH) becomes relatively small. Intraparticle diffusion into the columnar phase is strongly dependent on this concentration difference, and intraparticle diffusion into the columnar phase is suppressed. As a result, since the grain boundary diffusion proceeds preferentially, the heavy rare earth element RH can be effectively diffused into the sintered magnet body even if the supply amount of the heavy rare earth element RH to the surface of the magnet body is reduced.

On the other hand, in the case of the sintered magnet body in which the heavy rare earth element (RH) is not added in advance, the difference in concentration of the heavy rare earth element (RH) on the surface becomes relatively large, so that the intra-particle diffusion into the main phase is likely to occur, and the grain boundary diffusion. The ratio which becomes is low.

On the other hand, if the sintered magnet body before vapor deposition and diffusion contains 5 mass% or more of heavy rare earth elements (RH), the difference in concentration of heavy rare earth elements (RH) in the grain boundary becomes smaller, so that the coercive force by vapor deposition and diffusion is improved. The degree is lowered. Therefore, from the viewpoint of efficiently performing grain boundary diffusion of the heavy rare earth element (RH), the amount of the heavy rare earth element (RH) contained in the sintered magnet body before vapor deposition and diffusion is preferably 1.5 mass% or more and 3.5 mass% or less.

In the present embodiment, the sintered magnet body containing a predetermined amount of heavy rare earth element (RH) is further subjected to grain boundary diffusion of the heavy rare earth element (RH) from the surface of the sintered magnet body, whereby the light rare earth element is formed at the periphery. (RL) can be substituted with RH very efficiently. As a result, it becomes possible to raise coercive force H _cJ while suppressing the fall of residual magnetic flux density B _r .

(Embodiment 3)

In the method for producing an R-Fe-B rare earth sintered magnet according to the present embodiment, the sintering step of the R-Fe-B based rare earth magnet powder compact and the diffusion process of heavy rare earth elements (RH) are continuously performed in the same process chamber. . More specifically, first, a molded body of R-Fe-B-based rare earth magnet powder containing light rare earth element (RL) (at least one of Nd and Pr) as the main rare earth element (R) is referred to as heavy rare earth element (RH) ( The process (A) which arrange | positions in a process chamber facing a bulk body containing at least 1 sort (s) chosen from the group which consists of Dy, Ho, and Tb is performed.

Subsequently, the step (B) to produce an R-Fe-B rare earth sintered magnet body having an R ₂ Fe ₁₄ B type compound crystal grains by performing the sintering in the treatment chamber as a main phase. Thereafter, the bulk body and the R-Fe-B-based rare earth sintered magnet body are heated in the processing chamber, thereby feeding the heavy rare earth element (RH) from the bulk body to the surface of the R-Fe-B-based rare earth sintered magnet body. The step (C) of diffusing the rare earth element (RH) into the R-Fe-B system rare earth sintered magnet body is performed.

In this embodiment, since it is the same as that of Embodiment 1 except a sintering and diffusion process, only another process is demonstrated below.

[Sintering and Diffusion Process]

With reference to FIG. 2, the sintering and diffusion process in Embodiment 3 is demonstrated. FIG. 2 is a graph showing the time change of the atmospheric temperature and the atmospheric gas pressure in the processing chamber in the sintering and diffusion processes. FIG. In the graph, the dashed-dotted line represents the atmospheric gas pressure, and the solid line represents the atmospheric temperature.

First, the molded object of a magnetic powder and the RH bulk body are arrange | positioned in the process chamber 6 shown in FIG. 1, and pressure reduction is started (process A). Here, the molded object of a magnet powder is obtained by shape | molding the fine powder for rare earth sintered magnets produced by the well-known method by a well-known method.

After arranging the magnet powder compact and the RH bulk body in the processing chamber 6, the temperature in the processing chamber 6 is raised to a predetermined temperature in the range of 1000 ° C. to 1200 ° C. to start the sintering treatment. It is preferable to perform temperature rising after reducing the atmospheric gas pressure in the process chamber 6 to the pressure at the time of sintering (1 Pa-1 * 10 <^5> Pa). It is important to maintain the pressure during sintering at a relatively high level that can sufficiently suppress evaporation of the RH bulk body. As described above, since the evaporation rate of the heavy rare earth element (RH) from the RH bulk body is significantly suppressed when the pressure of the atmospheric gas is high, even if the powder compact and the RH bulk body coexist in the processing chamber 6, the atmospheric gas By controlling the pressure to an appropriate range, it becomes possible to advance the sintering process in a state where heavy rare earth element (RH) is not introduced into the powder compact.

A sintering process (process B) can be performed by hold | maintaining for 10 to 600 minutes in said atmosphere pressure and temperature range. In this embodiment, since the atmospheric gas pressure at the time of temperature rising and in process B is set to 1 Pa-1 * 10 <^5> Pa, sintering reaction advances rapidly in the state in which evaporation of RH bulk body was suppressed. If the atmospheric gas pressure in the step B is less than 1 Pa, evaporation of the heavy rare earth element (RH) proceeds from the RH bulk body, making it difficult to advance only the sintering reaction. On the other hand, if the atmospheric gas pressure in step B exceeds 1 × 10 ⁵ Pa, gas may remain in the powder compact during the sintering process, and voids may remain in the sintered magnet body. Therefore, it is preferable to set the atmospheric gas pressure in the process B in the range of 1 Pa to 1 × 10 ⁵ Pa, more preferably in the range of 5 × 10 ² Pa to 10 ⁴ Pa.

After completion of the sintering step (step B), the ambient temperature in the processing chamber 6 is dropped to 800 ° C. to 950 ° C. (step B ′ ₁ ). Thereafter, the atmospheric gas pressure is reduced to 1 × 10 ⁻⁵ Pa to 1 Pa (step B ′ ₂ ). The temperature suitable for the diffusion of the heavy rare earth element (RH) is 800 ° C to 950 ° C, and it is preferable to suppress evaporation of the RH bulk body in the process of reducing the temperature to this temperature range (step B ' ₁ ). In this embodiment, after lowering the atmosphere temperature at 800 ℃ ~ 950 ℃ discloses a reduction (step B _'2) of the atmospheric pressure. Therefore, after dropping to a temperature suitable for vapor deposition and diffusion, evaporation of the RH bulk body can be initiated, and the diffusion step C can be efficiently performed.

In the diffusion process C, the above-mentioned vapor deposition and diffusion are advanced by maintaining the atmospheric gas pressure at 1 × 10 ^-5 Pa to 1Pa and the process chamber temperature at 800 ° C to 950 ° C. In the diffusion process C, since grain boundary diffusion occurs preferentially by vapor deposition and diffusion, the formation of the intraparticle diffusion layer can be suppressed and the decrease in the residual magnetic flux density (B _r ) can be suppressed.

FIG. 3 is a graph showing a pressure temperature change different from the embodiment shown in FIG. 2. In the example shown in FIG. 3, the atmospheric gas pressure is lowered before the sintering step B is finished (step B ″ ₁ ). Then, after performing a heat treatment (step B ″ ₂ ) for 10 minutes to 300 minutes at an atmosphere gas pressure of 1 × 10 ⁻⁵ Pa to 1Pa and a temperature of 1000 ° C. to 1200 ° C. in the processing chamber, the temperature of the processing chamber 6 is 800 ° C. to Drop to 950 ° C. (step B ″ ₃ ). In the example of FIG. 3, since evaporation of RH bulk body is started in the middle of sintering process B, it becomes possible to shorten the whole time of a whole process.

On the other hand, the temperature raising before performing a sintering process does not need to be performed at a constant rate, as shown to FIG. 2 and FIG. You may add a process.

On the other hand, the diffusion process in this embodiment is insensitive to the surface condition of the sintered magnet body, and a film made of Al, Zn or Sn may be formed on the surface of the sintered magnet body before the diffusion process. This is because Al, Zn, or Sn is a low melting point metal, and if it is a small amount, it does not deteriorate the magnet characteristic and does not hinder the diffusion. Elements such as Al, Zn, and Sn may be contained in the RH bulk body.

As can be seen from the above description, in the present embodiment, grain boundary diffusion of the heavy rare earth element (RH) (at least one selected from the group consisting of Dy, Ho and Tb) is performed without greatly changing the conventional process. The heavy rare earth element (RH) can be supplied to a deep position inside the sintered magnet body, and the light rare earth element (RL) can be efficiently replaced with the heavy rare earth element (RH) at the columnar outer portion. As a result, it becomes possible to raise the coercive force H _cJ while suppressing the decrease in the residual low speed density B _r .

Example

(Example 1)

First, thickness 0.2mm to 0.3mm by the strip casting method using the alloy mix | blended so that it may have composition of Nd: 31.8, B: 0.97, Co: 0.92, Cu: 0.1, Al: 0.24, remainder: Fe (mass%). Alloy flakes were prepared.

This alloy flake was then filled into a vessel and housed in a hydrotreating apparatus. Then, the inside of the hydrotreating apparatus was filled in a hydrogen gas atmosphere at a pressure of 500 kPa to hydrogenate the alloy flakes at room temperature and then discharged. By performing such a hydrogen treatment, the alloy flakes were embrittled to produce an amorphous powder having a size of about 0.15 mm to 0.2 mm.

To the crude pulverized powder produced by the above hydrotreating, 0.05 wt% of zinc stearate was added as a grinding aid and mixed, followed by a pulverization step with a jet mill apparatus to produce a fine powder having a powder particle size of about 3 탆. .

The fine powder thus produced was molded by a press device to produce a powder compact. Specifically, the powder particles were pressed in a magnetic field oriented state in an applied magnetic field and pressed. Thereafter, the molded article was taken out of the press apparatus and sintered at 1020 占 폚 for 4 hours by a vacuum furnace. In this way, after producing a sintered compact block, the sintered compact block was mechanically processed, and the sintered magnet body of thickness 1mm x length 10mm x side 10mm was obtained.

The sintered magnet body was pickled with 0.3% nitric acid aqueous solution and dried, and then placed in a processing container having the configuration shown in FIG. 1. The processing container used in this embodiment is formed of Mo, and is provided with a member for supporting a plurality of sintered magnet bodies and a member for supporting two RH bulk bodies. The distance between the sintered magnet body and the RH bulk body was set to about 5 mm to 9 mm. The RH bulk body is formed of Dy having a purity of 99.9% and has a size of 30 mm x 30 mm x 5 mm.

Subsequently, the processing vessel of FIG. 1 was heated in a vacuum heat treatment furnace to perform heat treatment. The heat treatment conditions are as shown in Table 1 below. In addition, unless otherwise indicated below, heat processing temperature shall mean the temperature of a sintered magnet body and the RH bulk body substantially the same.

Condition Temperature
[° C] time
[minute] pressure
[Pa] X 900 30 1.0 × 10 ^-2 Y 180 Z 950

After the heat treatment was performed under the conditions shown in Table 1, an aging treatment (pressure 2 Pa, 60 minutes at 500 ° C) was performed.

Moreover, the sample which Al-coated (thickness: 1 micrometer) of the surface of the sintered magnet body by the barrel type electron beam heating vapor deposition method (output 16kW, 30 minutes) was also prepared, and it heat-processed on the conditions X and Y shown in Table 1. . After the heat treatment, an aging treatment (pressure 2 Pa, 60 minutes at 500 ° C) was performed.

For each sample, pulse magnetization of 3 MA / m was performed, and then the magnetic properties (residual magnetic flux density: B _r , coercive force: H _cJ ) were measured with a BH tracer. In addition, the diffusion state of Dy into the magnet was evaluated by EPMA (EPM-810 manufactured by Shimadzu Corporation). The residual magnetic flux density (B _r ) and coercive force (H _cJ ) obtained by the measurement are shown in Table 2 below.

Sample Al film Heat treatment condition B _r
[T] H _cJ
[kA / m] One none ^※ no spread 1.40 850 2 none X 1.40 1211 3 has exist X 1.39 1228 4 none Y 1.39 1402 5 has exist Y 1.38 1422 6 none Z 1.37 1601

In the comparative example of the sample 1, the aging process was performed on the same heat processing conditions as Sample 2-6, without performing Dy deposition and diffusion process. As can be seen from Table 2, in Samples 2 to 6 in which Dy diffusion in the present invention was performed, the coercive force (H _cJ ) was significantly improved compared to Comparative Example (Sample 1). In addition, in the samples 3 and 4 in which the Al film (1 μm in thickness) was formed on the surface of the sintered magnet body before diffusion, the presence of the Al film does not interfere with Dy diffusion, and the coercive force (H _cJ ) is improved. Able to know.

4 and 5 are photographs showing cross-sectional EPMA analysis results obtained for Samples 2 and 4, respectively. (A), (b), (c) and (d) of FIG. 4 are mapping photographs which show distribution of BEI (reflected electron beam image), Nd, Fe, and Dy, respectively. The same applies to FIG. 5, and the upper surface of each photograph corresponds to the surface of the sintered magnet body.

In FIG. 4 (d) and FIG. 5 (d), the portion where Dy is present at a relatively high concentration is shown brightly. As can be seen from these photographs, the region where Dy is present at a relatively high concentration is near the grain boundary. In the portion near the magnet surface, there are few regions where Dy is diffused at the same concentration near the grain boundary in the center of the columnar phase. According to the method of depositing a Dy film on the surface of a sintered magnet body and diffusing Dy into the inside of a sintered magnet body, many columnar phases in which Dy was diffused in high density | concentration are observed in the area | region near the surface of a sintered magnet body.

According to the present invention, Dy is not diffused in the central portion of the columnar phase (Nd ₂ Fe ₁₄ B-type compound crystal grain) even in the surface layer region from the surface of the sintered magnet body to a depth of 100 µm, and the Dy concentration at the central portion of the columnar phase is Dy near the grain boundary. Lower than concentration. This means that Dy diffused into the sintered magnet body through the grain boundary phase before the intra-particle diffusion in the surface layer region. Therefore, a rare earth sintered magnet having improved coercive force H _cJ can be obtained with almost no decrease in residual magnetic flux density B _r .

FIG. 6: shows the result of having measured Dy density | concentration in columnar center part and a grain boundary triple point about the sample 2 and the sample 3. FIG. Here, Dy density | concentration of columnar center part and a grain boundary triple point in sample 2 is represented by "◆" and "◇", respectively, and Dy density | concentration of the columnar center part and grain boundary triple point in sample 3 is respectively "●". 'And' ○ '.

In the region located about 50 mu m deep from the surface of the sintered magnet body, the Dy concentration at the center of the columnar phase is extremely low, while the Dy concentration at the grain boundary triple point is significantly increased. On the other hand, Dy was hardly detected in any sample in the region located at a depth of 500 mu m from the surface of the sintered magnet body.

FIG. 7 shows the results of measuring Dy concentrations in the columnar center and the grain boundary triple points for Samples 4 and 5. FIG. For the columnar central portions of the samples 4 and 5, the position where the Dy concentration was the highest was denoted by α and the position where the Dy concentration was the lowest by β. The Dy concentrations of the columnar center α, the columnar center β, and the grain boundary triple point in Sample 4 are represented by '◆', '△' and '◇', while the columnar center α and the columnar center β in Sample 5, respectively. And the Dy concentration at the grain boundary triple point are represented by '●', '□' and '○', respectively.

From the above results, a difference of 2 mol% (= 2 atomic%) or more in the Dy concentration occurred between the central portion of the columnar phase and the grain boundary phase in all samples.

(Example 2)

The sintered magnet body produced according to the method similar to the method demonstrated about Example 1 was prepared. The size was 7 mm x 7 mm x 3 mm. The magnetization direction was set to the thickness 3mm direction. The sintered magnet body was pickled with 0.3% nitric acid and dried, and then placed so as to face the Dy plate (30 mm x 30 mm x 5 mm, 99.9%) as shown in FIG.

Subsequently, the process container of FIG. 1 was heated in the vacuum heat processing furnace, and after heat processing on the conditions shown in Table 3, the aging process (60 minutes at 2Pa and 500 degreeC) was performed.

pressure
[Pa] 750 ℃ 800 ° C 850 ℃ 900 ℃ 950 ℃ 300 min 30min 120min 30min 1 × 10 ^-2 Sample
8 Sample
9 Sample
10 Sample
11 Sample
12 Sample
13 1.0 - - - Sample
14 - - 1 × 10 ² - - - Sample
15 - - 1 × 10 ⁵
Atmospheric pressure Ar
Flow - - - Sample
16 - -

On the other hand, the comparative example which performed the aging process on the conditions similar to Example 2 without performing a diffusion process is set to sample 7. After the aging treatment, the magnet properties (residual magnetic flux density (B _r ), coercive force (H _cJ )) were measured with a BH tracer. The measurement results are shown in Table 4 below.

Sample B _r
[T] H _cJ
[kA / m] 7 1.42 911 8 1.42 923 9 1.42 943 10 1.42 1079 11 1.42 1112 12 1.40 1352 13 1.40 1298 14 1.42 1143 15 1.42 1100 16 1.42 909

As can be seen from these results, in the present embodiment, even if the thickness of the sintered magnet body is 3 mm, the coercive force H _cJ is greatly improved without substantially reducing the residual magnetic flux density B _r .

8A and 8B are graphs showing the relationship between the processing temperature, the residual magnetic flux density B _r , and the coercive force H _cJ , respectively. As can be seen from these graphs, the coercive force H _cJ is increased with the increase of the processing temperature (pressure: 1 × 10 ⁻² Pa, time: 30 min). In the graph, 'pickling finish' refers to a sample in which the surface of the sintered magnet body is cleaned with 0.3% nitric acid and no film is formed on the surface, and 'Al coating' deposits an Al film on the sintered magnet body by electron beam heating deposition. Means a sample.

9A and 9B are graphs showing the relationship between the processing time, the residual magnetic flux density B _r , and the coercive force H _cJ , respectively. As can be seen from these graphs, the coercive force (H _cJ ) is increased with the increase of the treatment time (pressure: 1 × 10 ⁻² Pa, temperature: 900 ° C.). In the graphs, 'pickling finish' and 'Al coating' are as described above, and 'cut finish' means a cutting finish by a diamond cutter.

10A and 10B are graphs showing the relationship between the pressure in the processing vessel, the residual magnetic flux density B _r , and the coercive force H _cJ , respectively. The horizontal axis of the graph indicates the pressure of the argon gas atmosphere in the processing vessel. As can be seen from FIG. 10B, the coercive force H _cJ hardly depends on the pressure when the pressure is 1 × 10 ² Pa or less. When the pressure was 1 × 10 ⁵ Pa (atmospheric pressure), an improvement effect of the coercive force (H _cJ ) was not obtained. According to the EPMA analysis of the magnet surface, it was found that Dy was not deposited and diffused when the pressure in the processing container was atmospheric pressure. From this result, if the pressure in the processing atmosphere is sufficiently high, it is possible to prevent Dy from being deposited and diffused in the adjacent sintered magnet body even when the Dy plate is heated. Therefore, by controlling the atmospheric pressure, it is also possible to sequentially perform the sintering step and the Dy deposition / diffusion step in the same process chamber. That is, when performing a sintering process, sintering advances in the state in which the atmospheric pressure was fully raised and the deposition and diffusion of Dy from a Dy board were suppressed. Then, after the sintering is completed, the atmospheric pressure is lowered, whereby Dy can be supplied from the Dy plate to the sintered magnet body and further diffused. Thus, if the sintering process and the Dy diffusion process can be performed in the same apparatus, manufacturing cost can be reduced.

(Example 3)

In the present Example, the relationship between the Dy precipitation and the pressure (vacuum degree) of the processing atmosphere was examined. In the present Example, the Dy board (30 mm x 30 mm x 5 mm, 99.9%) was set in the inside using the container made from Mo (Mo pack) shown in FIG. Nb foil is adhere | attached on the inner wall of Mo pack. The Mo-pack shown in FIG. 11 was accommodated in a vacuum heat treatment furnace, and heat-processed for 180 minutes at 900 degreeC. The pressure (vacuum degree) inside the vacuum heat treatment furnace was made into 3 conditions of (1) 1 * 10 <^-2> Pa, (2) 1Pa, and (3) 150Pa.

It is a photograph which shows the external appearance observation result of the Mo pack inner wall after heat processing. The discolored portion on the inner wall of the Mopack is the Dy precipitation region. In the vacuum degree of (1), Dy is uniformly deposited in the whole inner wall area | region of Mo pack. In the vacuum degree of (2), Dy deposition occurs only in the vicinity of the Dy plate. In the vacuum degree of (3), the amount of Dy evaporation decreases and the area of the Dy deposition region is also reduced. On the other hand, Dy is hardly formed in the discoloration part, and it is guessed that Dy once attached to the discoloration part of an inner wall is vaporized again. By adjusting the vacuum degree of the heat treatment atmosphere in this manner, it is possible to control the evaporation rate (amount) and the precipitation region of Dy.

(Example 4)

The sintered magnet body and Dy plate (30 mm x 30 mm x 5 mm, 99.9%) produced by the method similar to the method described about Example 1 are arrange | positioned as shown in FIG. 13, and it is 900 degreeC in a vacuum heat processing furnace. 120 minutes of heat treatment were performed. The vacuum degree was set to three conditions of (1) 1 * 10 <^-2> Pa, (2) 1Pa, and (3) 150Pa.

Samples A to C of the sintered magnet body shown in FIG. 13 have a size of 7 mm x 7 mm x 3 mm (thickness: magnetization direction), and only sample D is 10 mm x 10 mm x 1.2 mm (thickness: magnetization direction). Has the size of. All of these sintered magnet bodies were subjected to heat treatment after pickling and drying with 0.3% nitric acid.

In addition, after the aging treatment was performed under conditions of 500 ° C., 60 minutes, and a vacuum degree of 2 Pa, magnet properties (residual magnetic flux density: B _r , coercive force: H _cJ ) were measured using a BH tracer. Table 5 has shown the data, such as the weight with respect to the sample A-the sample D, and the measurement result of a magnet characteristic with respect to the vacuum degree (1)-the vacuum degree (3).

① Weight before treatment
/ g Weight after treatment
/ g car
/ g area
/ Mm2 Growth rate
/ g / mm2 Sum
/ g yield
/% B _r
/ T H _cJ
/ kAm ^-1 Dy version 32.065 31.984 -0.081 2400 -3.4 × 10 ^-5 -0.081


45.7

- - Nb night 0.358 0.359 0.001 1552 6.4 × 10 ^-7

0.037

- - A 1.120 1.137 0.017 182 9.3 × 10 ^-5 1.41 1299 B 1.129 1.138 0.009 182 4.9 × 10 ^-5 1.41 1318 C 1.131 1.137 0.005 182 2.7 × 10 ^-5 1.41 1290 D 0.520 0.525 0.005 248 2.0 × 10 ^-5 1.41 1319 ② Weight before treatment
/ g Weight after treatment
/ g car
/ g area
/ Mm2 Growth rate
/ g / mm2 Sum
/ g yield
/% B _r
/ T H _cJ
/ kAm ^-1 Dy version 31.984 31.948 -0.036 2400 -1.5 × 10 ^-5 -0.036


77.8

- - Nb night 0.363 0.364 0.001 1552 6.4 × 10 ^-7

0.028

- - A 1.130 1.136 0.006 182 3.3 × 10 ^-5 1.41 1299 B 1.130 1.139 0.009 182 4.9 × 10 ^-5 1.41 1303 C 1.131 1.138 0.007 182 3.8 × 10 ^-5 1.41 1300 D 0.513 0.518 0.005 248 2.0 × 10 ^-5 1.41 1320 ③ Weight before treatment
/ g Weight after treatment
/ g car
/ g area
/ Mm2 Growth rate
/ g / mm2 Sum
/ g yield
/% B _r
/ T H _cJ
/ kAm ^-1 Dy version 33.668 33.662 -0.006 2400 -2.5 × 10 ^-6 -0.006


83.3

- - Nb night 0.352 0.353 0.001 1552 6.4 × 10 ^-7

0.005

- - A 1.131 1.132 0.001 182 5.5 × 10 ^-6 1.42 1164 B 1.130 1.131 0.001 182 5.5 × 10 ^-6 1.42 1192 C 1.128 1.129 0.001 182 5.5 × 10 ^-6 1.42 1180 D 0.512 0.513 0.001 248 4.0 × 10 ^-6 1.42 1200

As can be seen from Table 5, the properties of the sintered magnet bodies A to D were almost uniformly improved. On the other hand, the Dy yield was calculated | required from the weight change before and behind the heat processing shown in Table 5. Here, Dy yield is represented by ((Dy increase of Dy of a to-be-processed material (sintered magnet body or Nb foil)) / (reduction of Dy plate) x100. As the degree of vacuum lowered, the yield of Dy improved, which was about 83% at the degree of vacuum of (3). Moreover, the weight increase rate (per unit area) of Nb foil was remarkably low compared with the sintered magnet body in all the vacuum degrees ((1)-(3)). This indicates that, on the Nb surface that did not react (alloy) with Dy, the deposited Dy flew to the Nb surface and re-evaporated did not contribute to the Dy film formation on the Nb thin film. In other words, since Dy evaporated from the Dy plate is preferentially deposited and diffused on the sintered magnet body, the Dy yield is improved as compared with other known diffusion methods, thereby greatly contributing to resource saving.

(Example 5)

Example The method described for the first and the sintered magnet body is produced in a manner similar to the Dy plate (20㎜ × 30㎜ × 5㎜, 99.9 %) and also disposed as shown in the 14, 900 ℃, 1 × 10 ^{- The} heat treatment was performed under the condition of ² Pa. At this time, as shown in Table 6, the distance between the magnet and the Dy plate was changed. The sintered magnet body is obtained by pickling and drying 7 mm x 7 mm x 3 mm (thickness: magnetization direction) with 0.3% nitric acid. After the heat treatment, the aging treatment was performed under conditions of 500 ° C., 60 minutes, and 2 Pa, and the magnetic properties (residual magnetic flux density: B _r , coercive force: H _cJ ) were measured by a BH tracer.

X / mm 15 30 80 160 30min ① ② ③ - 120min - ④ ⑤ ⑥

As shown in Table 7 and FIG. 15, the degree of improvement of the coercive force changes depending on the distance between the sintered magnet body and the Dy plate. Although the improvement up to 30 mm is inferior, the improvement also becomes small when distance increases. However, even if the distance is 30 mm or more, the coercive force can be improved by extending the heat treatment time.

B _r
[T] H _cJ
[kA / m] B _r
[T] H _cJ
[kA / m] Circle material 1.42 911 ④ 1.41 1289 ① 1.42 1096 ⑤ 1.42 1255 ② 1.42 1102 ⑥ 1.42 1010 ③ 1.42 1033

(Example 6)

The sintered magnet body and Dy plate (30 mm x 30 mm x 5 mm, 99.9%) produced by the method similar to the method demonstrated about Example 1 are arrange | positioned as shown in FIG. 16, and it is 900 degreeC, in a vacuum heat treatment furnace, The heat treatment was performed under the condition of 1 × 10 ⁻² Pa. At this time, the arrangement of the Dy plates was heat-treated only in the case of top, bottom, and bottom. The sintered magnet body has a size of 7 mm x 7 mm x 3 mm (thickness: magnetization direction), pickled with 0.3% nitric acid and dried.

After the aging treatment was performed under the conditions of 500 ° C., 60 minutes, and 2 Pa, magnet characteristics (residual magnetic flux density: B _r , coercive force: H _cJ ) were measured with a BH tracer. 17 shows measurement results of magnet characteristics.

As shown in FIG. 17, the coercive force was improved irrespective of the arrangement of the Dy plates. This is considered to be because Dy vaporized during vacuum heat treatment is uniformly present near the surface of the sintered magnet body.

FIG. 18 shows the results of EPMA analysis on the surface of the sintered magnet body after heat treatment when the Dy plate is disposed only under the sintered magnet body. FIG. 18A is a photograph showing the analysis result at the center of the upper surface of the sintered magnet body, and FIG. 18B is a photograph showing the analysis result at the center of the lower surface of the sintered magnet body. In the center of the upper surface of the sintered magnet body, it can be seen that Dy is deposited and diffused almost in the same manner as the lower surface of the sintered magnet body. This means that the evaporated Dy is uniformly distributed near the surface of the sintered magnet body.

(Example 7)

The wet resistance test (80 degreeC, 90% RH) was performed about the sample which carried out vapor deposition and the diffusion process on condition X (900 degreeC * 30min) of Example 1. Fig. 19 is a photograph showing the rust occurrence of the surface of the magnet body after the wet resistance test, and the 'pickling finish' is an aging treatment (pressure 2Pa, without deposition and diffusion treatment) after pickling and drying the sintered magnet body with 0.3% nitric acid. 60 minutes at 500 ° C.), and '1-A' was pickled under the same conditions as 'acid pickling finish', followed by deposition, diffusion treatment, and aging treatment under the conditions X of Example 1, and '1-B'. Denotes that the Al coating is carried out under the same conditions as in Example 1 after pickling under the same conditions as the 'pickling finish', and the deposition, diffusion treatment, and aging treatment are performed under the condition X of Example 1. FIG. As can be seen from FIG. 19, compared with the sample of 'pickling finish', '1-A' and '1-B' are all improved in wet resistance. It is considered that the diffusion treatment according to the present invention forms a dense mixed phase structure of Dy or Nd, thereby increasing the uniformity of dislocations, and as a result, the potential difference corrosion becomes less likely to proceed.

(Example 8)

A 10 mm x 10 mm x 3 mm Nd sintered magnet of 31.8 Nd-bal.Fe-0.97B-0.92Co-0.1Cu-0.24Al (mass%) composition (Dy O% composition) produced under the conditions of Example 1 Cutting was carried out in the (magnetization direction). It arrange | positioned as shown in FIG. 20, and heat-processed 900 degreeC, 1 * 10 <^-2> Pa for 120 minutes. Thereafter, an aging treatment was performed at 500 ° C., 2 Pa for 120 minutes. Table 8 shows the composition of the Dy-X alloy.

Dy X Dy X mass% atom% Dy 100 0 100 0 Dy-Nd 50 50 47 53 Dy-al 25 75 67 33 Dy-Fe 88 12 72 28 Dy-in 85 15 80 20

Since Dy-Nd is a totally solid solution alloy, the composition ratio of Dy and Nd was 50:50 (mass%). For the other alloys, the composition ratio at which Dy and X make the process compound was chosen.

Magnetic properties (residual magnetic flux density (B _r ), coercive force (H _cJ )) of the samples before and after deposition and diffusion were measured with a BH tracer. 21A, 21B and 21C are graphs showing residual magnetic flux density B _r , coercive force H _cJ , and square ratio H _k / H _cJ, respectively. to be.

As can be seen from the graph of FIG. 21B, the coercive force (H _cJ ) was improved for all samples. This is because a Dy thickened layer having a high anisotropic magnetic field is formed in the outer portion of the columnar phase (Nd ₂ Fe ₁₄ B crystal) by Dy diffusion into the sintered magnet body. For Dy-X other than Dy-Al, the coercive force improvement is equivalent to that of Dy alone, but the decrease in residual magnetic flux density and square ratio (H _k / H _cJ ) was suppressed. This is because the melting point of the grain boundary can be lowered by depositing and diffusing not only Dy but also X elements, and it is estimated that diffusion of Dy is further promoted. This effect is remarkable when Nd is included as the element X. This is considered to be because the bulk body was able to replenish the trace amount of rare earth elements (Nd, Pr) evaporated from the grain boundary phase of the sintered magnet body by supplying Nd to the sintered magnet body.

On the other hand, in the same method as above, it was confirmed that similar effects also exist for elements (La, Ce, Cu, Co, Ag, Zn, Sn) other than the X element in Table 8.

(Example 9)

The sintered magnet body produced by the method similar to the method described about Example 1 was cut and obtained, and the sintered magnet body of 6 mm (magnetization direction) x 6 mm x 6 mm was obtained. This sintered magnet body and the Dy plate were arrange | positioned as shown to FIG. 22 (a). Specifically, a Dy plate was placed above and below the sintered magnet body, and the magnetization direction of the sintered magnet body was arranged so as to be substantially perpendicular to the opposing surface in the Dy plate above and below. The heat treatment for 120 minutes, 240 minutes, and 600 minutes was performed in 900 degreeC and 1 * 10 <^-2> Pa, respectively in the vacuum heat processing furnace in this arrangement state. Thereafter, an aging treatment was performed at 500 ° C., 2 Pa, and 120 minutes.

FIG.22 (b) is a figure which shows the crystal orientation of a sintered magnet body. In (b) of FIG. 22, the surface perpendicular | vertical to c-axis (magnetization direction) among the surfaces of the sintered magnet body which has a cubic shape is represented by the "aa plane", and the surface which is not perpendicular | vertical to the c-axis is represented by the "ac plane". have.

At the time of the said heat processing, in sample aa2, only two "aa faces" were exposed among the six faces of the sintered magnet body, and the other four faces were covered with Nb foil of 0.05 mm in thickness. Similarly, only two "ac faces" were exposed in sample ac2, and the other four faces were covered with Nb foil having a thickness of 0.05 mm.

Magnetic properties (residual magnetic flux density (B _r ), coercive force (H _cJ )) of the samples before and after the heat treatment were measured with a BH tracer.

FIG. 23 is a graph showing the amount of increase in coercive force H _cJ and the amount of decrease in residual magnetic flux density B _r . When the heat treatment time is 240 minutes or more, the sample aa and the sample ac have the same decrease in the residual magnetic flux density (B _r ), but the improvement in the coercive force (H _cJ ) is about 100 kA / m compared to the sample ac. Big.

Subsequently, the magnet properties were measured with a B-H tracer each time the sample aa2 and the sample ac2 were ground 0.2 mm from the surface using a sample of 240 minutes treatment to investigate the diffusion distance of Dy.

24 is a graph showing the coercive force H _cJ measured in this way. In the sample ac2, when the total grinding was about 0.6 mm, the coercive force (H _cJ ) is approximately equal to the value before the heat treatment. On the other hand, in the sample aa, when the total grinding was about 1.2 mm, the coercive force (H _cJ ) is approximately equal to the value before the heat treatment. As can be seen from the above, it can be seen that the diffusion speed in the c-axis direction (orientation direction) reaches about twice the diffusion speed in the direction perpendicular to this.

(Example 10)

A sintered magnet body as shown in Fig. 25A for a sintered magnet body having a thickness of 3 mm (magnetization direction) x 25 mm x 25 mm in size produced by the same method as described for Example 1 About 50% of the surface was covered with Nb foil. 1, it arrange | positioned and heat-processed for 120 minutes on 900 degreeC and 1 * 10 <^-2> Pa conditions in the vacuum heat processing furnace. Thereafter, an aging treatment was performed at 500 ° C., 2 Pa, and 120 minutes. Dy adhered to the Nb foil after the heat treatment was extremely small, and also reacted with the sintered magnet body and was not welded to the sintered magnet body so that it could be easily peeled off.

About the sample after the said heat processing, the part which has the size of thickness 3mm (magnetization direction) x 7mm in length x 7mm in width was cut out from the location shown in FIG.25 (b) by the diamond cutter. Then, the magnetic properties (residual magnetic flux density (B _r ), coercive force (H _cJ )) of the portion where Dy was diffused and penetrated (sample E) and the portion wrapped with Nb foil (sample F) were measured by a BH tracer.

The measurement results are shown in Table 9 below. It was confirmed that the coercive force (H _cJ ) was improved in the portion in which Dy was diffused and penetrated without being wrapped in Nb foil, compared to the portion wrapped in Nb foil. As described above, according to the present embodiment, it is possible to selectively diffuse Dy to a specific portion of the sintered magnet body and to change the magnetic properties of the portion differently from other portions.

Sample B _r
[T] H _cJ
[kA / m] E 1.40 1254 F 1.42 870

(Example 11)

First, alloy flakes having a thickness of 0.2 mm to 0.3 mm were produced by the strip casting method using ingots of alloys blended to have five kinds of compositions (L to P) shown in Table 10.

This alloy flake was then filled into a vessel and housed in a hydrotreating apparatus. Then, the inside of the hydrotreating apparatus was filled in a hydrogen gas atmosphere at a pressure of 500 kPa to hydrogenate the alloy flakes at room temperature and then discharged. By performing such a hydrogen treatment, the alloy flakes were embrittled, thereby producing an amorphous powder having a size of about 0.15 mm to 0.2 mm.

To the crude pulverized powder produced by the above hydrotreating, 0.05 wt% zinc stearate was added as a grinding aid and mixed, followed by a pulverization step using a jet mill apparatus to produce a fine powder having a particle size of about 3 탆.

The fine powder thus produced was molded by a press device to produce a powder compact. Specifically, press molding was performed by compressing the powder particles in a magnetic field-oriented state in an applied magnetic field. Thereafter, the molded article was taken out of the press apparatus and sintered at 1020 占 폚 for 4 hours by a vacuum furnace. After the sintered compact block was produced in this way, the sintered magnetic body of the dimension of Table 11 was obtained by mechanically processing this sintered compact block.

(mass%) Furtherance Nd Dy Fe B Co Cu Al L 32.0 0

bal



1.0



0.9



0.1



0.2

M 29.5 2.5 N 27.0 5.0 O 24.5 7.5 P 22.0 10.0

Condition Deposition Diffusion Conditions time Magnet dimensions alpha
1 × 10 ^-2 Pa
900 ℃
120 minutes
Thickness 3 mm x 7 mm x 7 mm β Thickness 6 mm x 7 mm x 7 mm gamma 240 minutes
Thickness 3 mm x 7 mm x 7 mm δ Thickness 6 mm x 7 mm x 7 mm

The sintered magnet body was pickled with 0.3% nitric acid aqueous solution and dried, and then placed in a processing vessel having the configuration shown in FIG. 1. The processing container used in this embodiment is formed of Mo, and is provided with a member for supporting a plurality of sintered magnet bodies and a member for supporting two RH bulk bodies. The distance between the sintered magnet body and the RH bulk body was set to about 5 mm to 9 mm. The RH bulk body is formed of a Dy plate having a purity of 99.9%, and has a size of 30 mm x 30 mm x 5 mm.

Next, the process container of FIG. 1 was heated in the vacuum heat treatment furnace, and heat processing for vapor deposition and diffusion was performed. The conditions of the heat treatment are as shown in Table 11. In addition, unless otherwise indicated, heat processing temperature shall mean the temperature of a sintered magnet body and the RH bulk body about the same.

After carrying out vapor deposition and diffusion under the conditions shown in Table 11, an aging treatment (pressure 2 Pa, 60 minutes at 500 ° C) was performed.

After performing pulse magnetization of 3 MA / m with respect to each sample before vapor deposition, diffusion, and an aging treatment, magnetic properties (magnetic force: H _cJ , residual magnetic flux density: B _r ) were measured with a BH tracer. By this measurement, the amount of change generated by vapor deposition and diffusion (aging treatment) was calculated for the coercive force (H _cJ ) and the residual magnetic flux density (B _r ) of the sample before vapor deposition and diffusion.

FIG. _26A is a graph showing the coercive force variation ΔH _cJ for the compositions L to P. FIG. The data points ◇, □, ◆ and ■ in the graph indicate the coercive force variation ΔH _cJ of the sample which was vapor-deposited and diffused under the conditions of α, β, γ and δ in Table 11, respectively.

26B is a graph which shows the residual magnetic flux density change amount (DELTA) B _r with respect to the composition L-the composition P. FIG. The data points ◇, □, ◆ and ■ in the graph indicate the residual magnetic flux density change amount ΔB _r of the sample which was deposited and diffused under the conditions of α, β, γ and δ in Table 11, respectively.

As can be seen from (a) and (b) of FIG. 26, the highest coercive force (H _cJ ) while suppressing the decrease of the residual magnetic flux density (B _r ) in the sintered magnet of composition B (Dy 2.5%) Could get

After performing cross-sectional polishing on the sample before vapor deposition and diffusion of Table 11, and the sample after vapor deposition and diffusion (after aging treatment), the analysis (ZAF method) by EPMA (EPM-1610 by Shimadzu Corporation) was performed. Table 12 below shows the amount of Dy (mass%) in the columnar center part and the grain boundary triple point part.

Composition L
Dy 0% Composition M
Dy 2.5% Composition N
Dy 5.0% Deposition diffusion
I'm Columnar 0 2.8 5.4 Grain boundary 0 5.5 8.2 Deposition diffusion
after Columnar 5.9 7.8 9.6 Grain boundary 16.2 27.5 29.0 Change
Columnar 5.9 5.0 4.2 Grain boundary 16.2 22.0 20.8

As can be seen from Table 12, the reason why excellent magnetic properties were obtained from the sample of the composition M can be estimated because Dy diffusion into the grain boundary phase can be most efficiently performed in the sample having the composition M.

(Example 12)

First, thickness 0.2mm by strip casting method using the ingot of the alloy mix | blended so that it may have composition of Nd: 31.8, B: 0.97, Co: 0.92, Cu: 0.1, Al: 0.24, remainder: Fe (mass%). A 0.3 mm alloy flake was produced.

This alloy flake was then filled into a vessel and housed in a hydrotreating apparatus. Then, the inside of the hydrotreating apparatus was filled in a hydrogen gas atmosphere at a pressure of 500 kPa to hydrogenate the alloy flakes at room temperature and then discharged. By performing such a hydrogen treatment, the alloy flakes were embrittled to produce an amorphous powder having a size of about 0.15 mm to 0.2 mm.

To the crude pulverized powder produced by the above hydrotreating, 0.05 wt% of zinc stearate was added as a grinding aid and mixed, followed by a pulverization step with a jet mill apparatus to produce a fine powder having a powder particle size of about 3 탆. .

The fine powder thus produced was molded by a press apparatus to produce a powder compact of 20 mm × 10 mm × 5 mm (magnetic field direction). Specifically, press molding was performed by compressing the powder particles in a magnetic field-oriented state in an applied magnetic field. Then, the molded object was taken out from the press apparatus and it arrange | positioned in the processing container which has the structure shown in FIG. The processing container used in the present embodiment is formed of Mo, and is provided with a member for supporting a plurality of molded bodies and a member for supporting two RH bulk bodies. The space | interval of a molded object and RH bulk body was set about 5 mm-9 mm. The RH bulk body is formed of a Dy plate having a purity of 99.9%, and has a size of 30 mm x 30 mm x 5 mm.

This processing container was accommodated in a vacuum furnace, and the sintering process and the diffusion process were performed under the conditions shown in Table 13. In Table 1, the conditions of the sintering and diffusion process regarding 12 samples of "1-A"-"6-B" are shown. "A" of Table 13 means the Example which heat-processed by arrange | positioning a powder compact with a Dy board as shown in FIG. In addition, "B" of Table 13 has shown the comparative example which heat-treated on the same conditions with respect to the powder molded object, without arrange | positioning a Dy board. All the samples were subjected to an aging treatment at 500 ° C., 2 Pa, and 120 minutes after the diffusion step.

Sintering process Heat treatment process Temperature 1040 ℃ 900 ℃ Vacuum degree 10 ³ Pa 150 Pa 1 × 10 ^-2 Pa 1 × 10 ^-2 Pa 1-A -
180 minutes
-
120 minutes (diffusion)
120 minutes (no diffusion) 1-B 2-A -
120 minutes
60 minutes
60 minutes (diffusion)
60 minutes (no diffusion) 2-B 3-A -
90 minutes
90 minutes
30 minutes (diffusion)
30 minutes (no diffusion) 3-B 4-A 180 minutes
-
-
120 minutes (diffusion)
120 minutes (no diffusion) 4-B 5-A 120 minutes
-
60 minutes
60 minutes (diffusion)
60 minutes (no diffusion) 5-B 6-A 90 minutes
-
90 minutes
30 minutes (diffusion)
30 minutes (no diffusion) 6-B

For each obtained sample, the magnetic properties (residual magnetic flux density (B _r ), coercive force (H _cJ )) were measured with a BH tracer.

(A) is a graph which shows the measured value of the residual magnetic flux density (B _r ) about 12 samples, and FIG. 27 (b) is a graph which shows the measured value of the coercive force (H _cJ ) regarding the sample. .

As can be seen from these figures, the coercive force (H _cJ ) for all the examples (1-A, 2-A, 3-A, 4-A, 5-A, 6-A) is shown in Comparative Example (1). It can be seen that the coercive force (H _cJ ) of -B, 2-B, 3-B, 4-B, 5-B, 6-B) is significantly higher. Especially in sample 4-A, the rate of decrease of the residual magnetic flux density (B _r ) is the lowest. This indicates that when the evaporation diffusion of Dy is started after completion of sintering at a relatively high atmospheric pressure, Dy diffuses most effectively into the grain boundary phase and effectively increases the coercive force (H _cJ ).

(Example 13)

First, a sintered magnet body was produced in the same manner as in Example 1 using an alloy blended to have a composition of Nd: 32.0, B: 1.0, Co: 0.9, Cu: 0.1, Al: 0.2, and balance: Fe (mass%). . This sintered magnet body was cut into 7 mm x 7 mm x 3 mm size.

In the structure shown in FIG. 1, heat processing was performed using the Tb board as the RH bulk body 4. The heat treatment was performed at 900 ° C. or 950 ° C., 1 × 10 ⁻³ Pa for 120 minutes. Thereafter, an aging treatment was performed at 500 ° C., 2 Pa, and 120 minutes.

The magnetic properties (residual magnetic flux density (B _r ) and coercive force (H _cJ )) of the samples before and after deposition and diffusion were measured by the BH tracer, and the magnetic properties of the magnet body before deposition and diffusion were B _r = 1.40T, H _cJ = 850 kA / m and the magnetic properties of the magnet body after vapor deposition and diffusion were B _r = 1.40T, H _cJ = 1250 kA / m, B _r = 1.40T, and H _cJ = 1311 kA / m, respectively.

From this result, it can be confirmed that the coercive force H _cJ can be improved by lowering the residual magnetic flux density B _r by depositing and diffusing Tb.

(Example 14)

A sample of the sintered magnet body was produced in the same manner as in Example 13 above. After arrange | positioning as shown in FIG. 1, vapor deposition and the diffusion were performed from the RH bulk body 4 which consists of Dy from the sintered magnet body. Specifically, heat treatment was performed at 900 ° C., 1 × 10 ⁻² Pa, 60 minutes or 120 minutes.

Some samples were subjected to an aging treatment at 500 ° C., 2 Pa for 120 minutes after vapor deposition and diffusion. The remaining samples were subjected to heat treatment at 900 ° C., 1 × 10 ⁻² Pa, and 120 minutes with the RH bulk body 4 removed in the configuration shown in FIG. 1, followed by aging treatment at 500 ° C., 2 Pa and 120 minutes. It was. Thereafter, magnetic properties were measured with the BH tracer for each of the above samples. The measurement results are shown in Table 14.

Deposition Diffusion Time
[min] No additional heat treatment With additional heat treatment B _r [T] H _cJ [kA / m] B _r [T] H _cJ [kA / m] Circle material - 1.40 850 1.40 870 G 60 1.39 1150 1.39 1250 H 120 1.39 1220 1.39 1370

It can be seen that by applying additional heat treatment, the coercive force is further improved.

According to the present invention, the columnar crystal grains in which heavy rare earth elements (RH) are efficiently concentrated can be efficiently formed inside the sintered magnet body, so that a high-performance magnet having high residual magnetic flux density and high coercive force can be provided. have.

Claims (16)

R- having a main phase of R ₂ Fe ₁₄ B compound crystal grains containing light rare earth element (RL), which is at least one of Nd and Pr, as a main rare earth element (R) (A) preparing a Fe-B-based rare earth sintered magnet body, Disposing a bulk body containing at least one heavy rare earth element (RH) selected from the group consisting of Dy, Ho, and Tb together with the R-Fe-B-based rare earth sintered magnet body in a process chamber (b )Wow, By heating the process chamber in which the bulk body and the R-Fe-B-based rare earth sintered magnet body are disposed to 700 ° C. or more and 1000 ° C. or less, heavy rare earth elements (RH) are sintered from the bulk body to the R-Fe-B-based rare earth sintering. (C) diffusing the heavy rare earth element (RH) into the R-Fe-B-based rare earth sintered magnet body while supplying it to the surface of the magnet body, The said (c) WHEREIN: The manufacturing method of the R-Fe-B rare earth sintered magnet whose temperature difference of the temperature of the said R-Fe-B rare earth sintered magnet body and the said bulk body temperature is less than 20 degreeC. The method of claim 1, In the said process (c), the said bulk body and the said R-Fe-B system rare earth sintered magnet body are arrange | positioned in the said process chamber, without contacting, and R- which sets the average space within the range of 0.1 mm or more and 300 mm or less. Method for producing Fe-B rare earth sintered magnet. delete The method of claim 1, In the above step (c), The method of the atmosphere gas pressure of 10 ^-5 Pa ~ 500Pa adjusted based rare-earth sintered R-Fe-B magnet in the range of in the treatment chamber. The method of claim 1, In the step (c), the R-Fe-B-based rare earth sintered magnet which maintains the temperature of the bulk body and the R-Fe-B-based rare earth sintered magnet body within a range of 700 ° C to 1000 ° C for 10 minutes to 600 minutes. Method of preparation. The method of claim 1, The sintered magnet body contains 0.1 to 5.0 mass% of heavy rare earth elements (RH), The heavy rare earth element (RH) is at least one member selected from the group consisting of Dy, Ho, and Tb. The method according to claim 6, The said sintered magnet body is a manufacturing method of the R-Fe-B rare earth sintered magnet whose content of a heavy rare earth element (RH) is 1.5 mass% or more and 3.5 mass% or less. The method of claim 1, The bulk contains an alloy of heavy rare earth element (RH) and element X, The element X is at least one member selected from the group consisting of Nd, Pr, La, Ce, Al, Zn, Sn, Cu, Co, Fe, Ag and In. 9. The method of claim 8, The element X is a method for producing an R-Fe-B rare earth sintered magnet is at least one selected from Nd and Pr. The method of claim 1, R-Fe-B-based rare earth comprising the step of performing an additional heat treatment for 10 to 600 minutes at a temperature of 700 ℃ to 1000 ℃ to the R-Fe-B-based rare earth sintered magnet body after the step (c) Method of manufacturing sintered magnets. delete delete delete delete delete An R-Fe-B-based rare earth sintered magnet mainly composed of R ₂ Fe ₁₄ B-type compound grains containing light rare earth element (RL) of Nd and Pr as the main rare earth element (R), and diffusing grain boundaries from the surface The R ₂ Fe ₁₄ B-type compound crystal grains containing at least one heavy rare earth element (RH) selected from the group consisting of Dy, Ho, and Tb introduced into the inside, in a surface layer region from the surface to a depth of 100 μm; R-Fe-B rare earths having a concentration of heavy rare earth elements (RH) at the grain boundary of 1 atomic% or more higher than the concentration of heavy rare earth elements (RH) at the central portion of the R ₂ Fe ₁₄ B compound crystal grains Sintered magnet.

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